CN101682995A

CN101682995A - Production is by the method for the substrate laminated material of washing

Info

Publication number: CN101682995A
Application number: CN200880017048A
Authority: CN
Inventors: R·洛赫特曼; J·卡祖恩; N·瓦格纳; J·普菲斯特; D·亨切尔
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2007-05-24
Filing date: 2008-05-20
Publication date: 2010-03-24
Also published as: CA2685517A1; BRPI0811243A2; JP2010527811A; US20100176090A1; TW200902304A; RU2009147813A; IL201633A0; KR20100016622A; WO2008142064A1; EP2153708A1

Abstract

The present invention relates to a kind of production have the carrier (51) made by non-conductive material (37), by the method for the substrate laminated material of washing, applied by metal coating (25,53) at least one side of described carrier.In the first step, with dispersion (5) basic coating (11) is administered on the base material (3), described dispersion (5) contains can not have that electropaining is covered and/or particle that electrolysis applies in basis material.Solidify at least in part and/or dry described basis material.Cover and/or electrolysis is coated in basic coating (11) and go up forms metal coating by no electropaining.To be laminated on the metal coating (25) by the carrier (51) that make non-conductive material (37).As final step, remove carrier (51) and the metal coating of lamination (25) and at least a portion base coating (11) thereon from base material (3).

Description

Production is by the method for the substrate laminated material of washing

The present invention relates to a kind of production have the carrier made by non-conductive material, by the method for the substrate laminated material of washing, applied by metal level at least one side of described carrier.

These substrate laminated materials by washing for example are used to produce electronic printing circuit board.In this case, the conductor line structure is made of metal level, removes the unwanted part of conductor line structure for this reason.For electric current can not be flow through by the carrier in the substrate laminated material of washing, this carrier is made by non-conductive material.

Generally speaking, in order to produce copper-plated substrate laminated material, for example glass fabric also only carries out partly solidified with the batching dipping of mainly being made up of epoxy resin.These partly solidified substrate laminated materials are called " prepreg ".They are alternately isolated to form stacked body by Copper Foil.Copper Foil mainly is so-called ED type (ED=electro-deposition).Their thickness is between the 9-400 micron, but major part is between the 12-72 micron.The stacked body of this isolation is placed between two substrate steel discs subsequently, promptly so-called compressing tablet.A plurality of stacked bodies that these contain sheet metal, Copper Foil, prepreg, Copper Foil and sheet metal are separately suppressed under the pressure of 120-250 ℃ temperature and 5-30 crust subsequently.Thereby the epoxy resin full solidification that glass fibre strengthens.Simultaneously, each substrate laminated material that so forms is by the steel disc smoothing.

Because the production of thin copper foil is very expensive, so the substrate laminated material by washing of Sheng Chaning also is very expensive in this way.In addition, thickness less than 10 microns, especially be unusual difficulty or impossible less than the processing of 5 microns Copper Foil, this is because Copper Foil is torn.For thin copper foil, be thickness less than for 12 microns the Copper Foil, the always extra thicker Copper Foil (thickness that generally has 18 microns or 36 microns) that uses is as carrier.For copper is discharged from carrier, generally thin chromium layer is as separating layer.

The purpose of this invention is to provide a kind of can directly production by the method for the substrate laminated material of washing, these laminated materials have had extremely thin base copper, and do not need extra metal forming as carrier.

This purpose have by a kind of production the carrier made by non-conductive material, realized that by the method for the substrate laminated material of washing applied by metal level at least one side of described carrier, the method may further comprise the steps:

(a) with dispersion basic unit is administered on the base material, described dispersion contains can not have that electropaining is covered and/or particle that electrolysis applies in basis material,

(b) solidify at least in part and/or dry described basis material,

(c) cover by no electropaining and/or electrolysis is coated in and forms metal level in the basic unit,

(d) will be pressed onto by the carrier layer that non-conductive material is made on the metal level that in step (c), makes,

(e) remove with the carrier of metal level lamination and at least a portion basic unit randomly from base material.

The advantage of the inventive method is can use metal level simultaneously in an operating procedure when production substrate laminated material.Not to use the paper tinsel that to tear.In addition, even Bao metal level also can be used by the inventive method especially.

The advantage of using described base material is that this base material is capable of circulation, and this is because general this base material does not damage after removing coated substrate laminated material.In addition, also base material be can produce, thereby can predetermined surface quality and surface texture for coated substrate laminated material, be realized according to the surface appearance of base material with particular surface quality and surface texture.

Base material for example is sheet or paper tinsel.Paper tinsel is preferably soft.In order to discharge metal level and optional a part of basic unit from base material, base material is preferably applied by release agent.Select as another kind, base material can be sheet or the paper tinsel of being made by release agent.Under the situation of continuous processing control, base material preferably provides as paper tinsel, and described paper tinsel is applied by release agent or made by release agent, and it is stored on the roller as so-called paper tinsel for no reason.The method can be used as volume to volume technology carries out, and wherein takes off paper tinsel from roller, carries out at least one processing step, and preferably carries out all processing steps, and then reel.

All can be suitable as the material of base material by the material that applied pressure during lamination and the required temperature of curing materials are damaged.Base material preferably is made of metal, the steel disc in for example conventional field, aluminium, solid aluminium alloy or solid copper alloy.

If the lamination of the carrier in step (d) is to carry out under the temperature higher than ambient temperature, the material that then preferably is used for base material should be good heat conductor.From the heat transfer of base material to stacked body inside is according to selected material type, regulates by the heating curves of laminating machine.Under the situation of the static press of hydraulic pressure, regulate by outside sheet, adding material in addition to the heat transfer of stacked body inside, for example multi-ply paper.Thereby realized the even curing of carrier material.

In the first step, the dispersion of nano-particles body that electropaining is covered and/or electrolysis applies that can not have that will contain in basis material is administered on the base material.And have between the surface of the base material that is applied by release agent high cohesive force and and the dispersion used between have a low cohesive force all material be suitable as the release agent that is used for coated substrate.Those skilled in the art will select suitable release agent according to the composition of dispersion.Release agent can be a suitable polymers, for example polyvinyl alcohol, organosilicon polymer or fluoropolymer, or low-molecular-weight fat, wax or oil.The release agent that has less than the 30mN/m low surface tension with respect to air is preferred.These are fluoropolymers for example, for example polytetrafluoroethylene (PTFE), polyvinylidene fluoride, polyvinyl fluoride (PVF), ethylene-tetrafluoroethylene copolymer (EFE), poly--4-methylpentene-1 (TDX), modified poly ester (Pacothane for example ^TM, from PacothaneTechnologies), or organosilicon polymer, the cellulose triacetate of for example polydimethylsiloxanepolymer polymer, and modification (CTA).Be polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), ethylene-tetrafluoroethylene copolymer (EFE), poly--4-methylpentene-1 (TDX), modified poly ester (Pacothane for example especially preferably as release agent ^TM, from Pacothane Technologies) and the cellulose triacetate (CTA) of modification.According to the temperature during the lamination in step (d), also can use native paraffin or synthetic wax and semi-synthetic wax, for example polyolefin-wax or polyimides wax.The combination of different release agents also is possible.

Can release agent coating be administered on the sheet metal by well known to a person skilled in the art method.For example, can provide base material with permanent release agent coating.For this reason, roughened is generally at first carried out on the surface.Fluorine-containing release agent, for example PTFE for example forever uses by plasma method.Release agent also can be administered on the surface by the solution that contains release agent.Solution discharges release agent by evaporating from then on.

Select as another, also can use the release agent coating that does not have with the base material permanent adhesive.

Release agent coating can be used by well known to a person skilled in the art any application process.For example, also can be coated with by scraper coating, roller coat, spraying, lacquer, method such as brushing uses release agent coating.But, preferably release agent coating is administered on the base material, for example referring to the PTFE paint-on technique by known plasma method.

Select as another, under the situation of so-called plasma method, plasma method is used for for example having the coating of PTFE and is well known to a person skilled in the art, welds by arc discharge and uses releasing agent layer.

If release agent coating is not to be glued fast on the base material, then necessary respectively is to use this coating before dosed dispersion once more, and described dispersion contains can not have the particle that electropaining is covered and/or electrolysis applies.

Can not have that electropaining is covered and/or particle that electrolysis applies can be not had material, different the not having mixtures of material that electropaining is covered and/or electrolysis applies that electropaining is covered and/or electrolysis applies and maybe can not had material that electropaining is covered and/or electrolysis applies and the mixtures of material particle that make, that have any geometry that can not so apply by any.Suitable not have the material that electropaining is covered and/or electrolysis applies for example be: carbon for example is the form of carbon black, graphite, Graphene or carbon nano-tube; The conducting metal complex, the polymer of conductive organic compound or conduction or metal, preferred zinc, nickel, copper, tin, cobalt, manganese, iron, magnesium, lead, chromium, bismuth, silver, gold, aluminium, titanium, palladium, platinum, tantalum and their alloy, or contain the metal mixture of at least a these metals.Suitable alloy is for example CuZn, CuSn, CuAg, CuNi, SnPb, SnBi, SnCo, NiPb, ZnFe, ZnNi, ZnCo and ZnMn.Particularly preferably be aluminium, iron, copper, silver, nickel, zinc, carbon and their mixture.

Can not have that electropaining is covered and/or particle that electrolysis applies preferably has the mean particle diameter of 0.001-100 micron, preferred 0.002-50 micron, preferred especially 0.005-10 micron.Mean particle diameter can be determined by the laser diffraction detection method, for example use Microtrac X100 equipment.Their production method is depended in the distribution of particle diameter.Diameter distributes and contains only maximum usually, but a plurality of maximums also are possible.Therefore, for example can be with mean particle diameter less than 100 microns particle and mean particle diameter mix particles greater than 1 micron, thus obtain denser particle filling.

Can not have that electropaining is covered and/or the surface of the particle that electrolysis applies can have coating at least in part.Suitable coating compounds can be inorganic (SiO for example ₂, phosphate) or organically.Certainly, conducting particles also can be by metal or metal oxide-coated.Metal also can exist with the form of partial oxidation.

If two or more different metals will form and describedly can not have that electropaining is covered and/or particle that electrolysis applies, then this can use the mixture of these metals to carry out.Especially, preferable alloy is selected from aluminium, iron, copper, nickel, silver or zinc.

Can not have the particle that electropaining is covered and/or electrolysis applies and can contain first metal and second metal yet, wherein there be (with the alloy of first metal or one or more other metals) in second metal with the form of alloy, maybe can not have the particle that electropaining is covered and/or electrolysis applies and can contain two kinds of different alloys.

Except selecting not have the particle that electropaining is covered and/or electrolysis applies, can not have that electropaining is covered and/or the shape of the particle that electrolysis applies is also influential to the dispersion performance after applying.At vpg connection, well known to a person skilled in the art that many schemes are feasible.Can not have that electropaining is covered and/or the shape of the particle that electrolysis applies can for example be needle-like, cylindrical, platelet-shaped or sphere.These shapes of particle have been represented Utopian shape, and actual shape may have difference more or less, is for example caused by production.For example, the tear drop shape particle is that interior the actual of idealized sphere of the scope of the invention departed from.

Have various shapes of particle can not have that electropaining is covered and/or particle that electrolysis applies is commercially available.

Can not have that electropaining is covered and/or during the mixture of the particle that electrolysis applies, each blending ingredients also can have different shapes of particle and/or particle size when using.Only also can use one type have different particle sizes and/or a shape of particle can not have that electropaining is covered and/or the mixture of the particle that electrolysis applies.Under the situation of different shapes of particle and/or particle size, metallic aluminium, iron, copper, silver, nickel and zinc and carbon also are preferred.

As mentioned above, not having the particle that electropaining is covered and/or electrolysis applies can add in the dispersion with form of powder.These powder for example metal dust are commercially available commodity, maybe can prepare by known method, for example carry out electrolytic deposition or electronation by solution from slaine, or by for example using the hydrogen reducing oxide powder, or by spraying or atomization metal melt, particularly in cooling agent, for example gas or water.The atomizing of gas and water and the reduction of metal oxide are preferred.Metal dust with preferable particle size also can be by grinding general thicker metal dust production.For example ball milling is applicable to this purpose.Except the atomizing of gas and water, preferred carbonyl-iron powder technology of producing carbonyl-iron powder under the situation of iron.This thermal decomposition by iron pentacarbonyl is carried out.This for example is described in Ullmann ' sEncyclopedia of Industrial Chemistry, and the 5th edition, A14 volume, 599 pages.The decomposition of iron pentacarbonyl can for example be carried out in heatable decomposer under high temperature and high pressure, decomposer comprises fire resisting material tube on preferred vertical position, for example quartz glass or V2A steel, described pipe is heated instrument and surrounds, and for example comprises the heating jacket of heating bath, heating electric wire or circulation heat medium.Carbonyl-nickel by powder also can prepare by similar methods.

Scutellate can not have that electropaining is covered and/or particle that electrolysis applies can be by the control of the optimal conditions in preparation process, or obtain behind mechanical treatment, for example by handling in the blender ball milling.

Based on the total weight meter of dry coating, can not have that electropaining is covered and/or the ratio of the particle that electrolysis applies 20-98 weight % preferably.Can not have that electropaining is covered and/or the preferred proportion scope of the particle that electrolysis applies is 30-95 weight %, based on the total weight meter of dry coating.For example, suitable basis material is the adhesive with pigment compatibility anchor group, natural and synthetic polymer and derivative thereof, natural resin and synthetic resin and their derivative, natural rubber, synthetic rubber, protein, cellulose derivative, the wet goods of dry and non-drying.They can (but not necessarily) carry out chemistry or physical solidification, for example air curing, radiation curing or temperature-curable.

Basis material is polymer or blend polymer preferably.

Preferably the polymer as basis material for example is: ABS (acrylonitrile-butadiene-styrene (ABS)); ASA (acrylonitrile-styrene-acrylic ester); Acrylate; Alkyd resins; The alkyl vinyl acetic acid esters; Alkyl vinyl acetate copolymer, particularly methylene vinyl acetate, ethylidene vinyl acetate, butylidene vinyl acetate; The alkylidene vinyl chloride copolymer; Amino resins; Aldehyde and ketone resin; Cellulose and cellulose derivative, particularly hydroxy alkyl cellulose, cellulose esters, for example acetic acid esters, propionic ester, butyrate, carboxyalkyl cellulose, celluloid; Epoxy acrylate; Epoxy resin; Modified epoxy, for example difunctionality or polyfunctional bisphenol-A or Bisphenol F resin, epoxy-novolac resin, brominated epoxy resin, cycloaliphatic epoxy resin; Aliphatic epoxy resin, glycidol ether, vinyl ethers, ethylene-acrylic acid copolymer; Hydrocarbon resin; MABS (transparent ABS also contains acrylic ester unit); Melamine resin, copolymer-maleic anhydride; Methacrylate; Natural rubber; Synthetic rubber; Chlorine rubber; Natural resin; Abietic resin; Lac; Phenol resin; Phenoxy resin; Polyester; Mylar, for example phenylester resin; Polysulfones; Polyether sulfone; Polyamide; Polyimides; Polyaniline; Polypyrrole; Polybutylene terephthalate (PBT); Merlon (for example

From Bayer AG); Polyester acrylate; Polyether acrylate; Polyethylene; The polyethylene thiophene; Polyethylene Naphthalate; Polyethylene terephthalate (PET); Polyethylene terephthalate glycol (PETG); Polypropylene; Polymethyl methacrylate (PMMA); Polyphenylene oxide (PPO); Polystyrene (PS), polytetrafluoroethylene (PTFE); PolyTHF; Polyethers (for example polyethylene glycol, polypropylene glycol); Polyvinyl compound, particularly polyvinyl chloride (PVC), PVC copolymer, PVdC, polyvinyl acetate, and their copolymer, the polyvinyl alcohol of optional part hydrolysis, polyvinyl acetal, polyvinyl acetate, PVP, polyvingl ether, in solution and as polyvinylacrylate and the polymethyl vinyl acetate and their copolymer of dispersion, polyacrylate and polystyrene copolymer, for example polystyrene/maleic anhydride block copolymer; Polystyrene (modification or not impact-resistant modified); Polyurethane, uncrosslinked or with isocyanate-crosslinked; Urethane acrylate; The styrene/acrylic analog copolymer; Styrene/butadiene block copolymer (for example

Or

From BASF AG; K-Resin ^TM, from CPC); Protein, for example casein; Styrene-isoprene block copolymer; Cyanate resin, bismaleimides-cyanate resin (BT), cyanate ester resin (CE), allylation polyphenylene oxide (APPE).Two or more mixture of polymers also can form basis material.

Especially preferably the polymer as basis material is an acrylate, acrylic resin, cellulose derivative, methacrylate, methacrylic resin, melamine resin, amino resins, polyolefin, polyimides, epoxy resin, modified epoxy, for example difunctionality or polyfunctional bisphenol-A or Bisphenol F resin, epoxy-novolac resin, brominated epoxy resin, cycloaliphatic epoxy resin; Aliphatic epoxy resin, glycidol ether, vinyl ethers and phenol resin, polyurethane, polyester, polyvinyl acetal, polyvinyl acetate, polystyrene, polystyrene copolymer, the polystyrene acrylate, styrene/butadiene block copolymer, cyanate resin, bismaleimides-cyanate resin (BT), alkenyl vinyl acetate and vinyl chloride copolymer, polyamide and their copolymer.Two or more these mixture of polymers also can form basis material.

Basis material can for example contain in addition and well known to a person skilled in the art crosslinking agent and catalyst, for example the polyamines of light trigger, tertiary amine, imidazoles, aliphatic series and aromatics, polyamino amine, acid anhydrides, BF ₃-MEA, phenol resin, phenylethylene-maleic anhydride polymer, hydroxy acrylate, dicyandiamide or polyisocyanates.

As the basis material that in producing printed circuit board (PCB), is used for dispersion, preferably use the resin of thermal curable or radiation-hardenable, for example modified epoxy, for example difunctionality or polyfunctional bisphenol-A or Bisphenol F resin, epoxy-novolac resin, brominated epoxy resin, cycloaliphatic epoxy resin; Aliphatic epoxy resin, glycidol ether, cyanate, vinyl ethers, phenol resin, phenoxy resin, polyimides, melamine resin, amino resins, cyanate resin, bismaleimides-cyanate resin (BT), polyurethane, polyester and cellulose derivative.

Based on the total weight meter of dry coating, the ratio of organic bond component is 0.01-60 weight %.This ratio is 0.1-45 weight % preferably, more preferably 0.5-35 weight %.

Be administered on the carrier that is applied by release agent in order to contain basis material and not have the dispersion of nano-particles body that electropaining is covered and/or electrolysis applies, can in this dispersion, add solvent or solvent mixture in addition, thereby regulate the dispersion viscosity that is applicable to each application process.Suitable solvent is aliphatic series and the hydrocarbon of an aromatics (normal octane for example for example, cyclohexane, toluene, dimethylbenzene), alcohol (methyl alcohol for example, ethanol, the 1-propyl alcohol, the 2-propyl alcohol, the 1-butanols, the 2-butanols, amylalcohol), polyalcohol (glycerine for example, ethylene glycol, propylene glycol, neopentyl glycol), Arrcostab (methyl acetate for example, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, isopropyl acetate, the 3-methyl butanol), alkoxyl alcohol (methoxypropanol for example, methoxybutanol, the ethyoxyl propyl alcohol), alkyl benzene (ethylo benzene for example, cumene), butyl glycol, dibutyl ethylene glycol, the acetic acid esters of alkyl glycol (butyl glycol acetate for example, dibutyl ethylene glycol ethyl ethers acid esters), dimethyl formamide (DMF), diacetone alcohol, the diethylene glycol (DEG) dialkyl ether, the diglycol monotertiary alkyl ether, the dipropylene glycol dialkyl ether, the dipropylene glycol monoalky lether, diethylene glycol (DEG) alkyl ether acetic acid esters, dipropylene glycol alkyl ether acetic acid esters diox, dipropylene glycol and ether, diethylene glycol (DEG) and ether, DBE (dibasic ester), ether (ether for example, oxolane), dichloroethanes, ethylene glycol, the ethylene glycol ethyl ethers acid esters, the ethylene glycol dimethyl ester, cresols, lactone (for example butyrolactone), ketone (acetone for example, the 2-butanone, cyclohexanone, methyl ethyl ketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK)), the dimethyl glycol, carrene, methylene ethylene glycol, the methylene glycol acetic acid esters, sylvan (adjacent-, between-, p-Cresol), pyrrolidones (for example N-N-methyl-2-2-pyrrolidone N-), propylene glycol, propylene carbonate, carbon tetrachloride, toluene, trimethylolpropane (TMP), aromatic hydrocarbon and mixture, aliphatic hydrocarbon and mixture, alcohols monoterpene (for example terpineol), water, and the mixture of above-mentioned two or more these solvents.

Preferred solvent is an alcohol (ethanol for example, the 1-propyl alcohol, the 2-propyl alcohol, butanols), alkoxyl alcohol (methoxypropanol for example, the ethyoxyl propyl alcohol, butyl glycol, dibutyl ethylene glycol), butyrolactone, the diethylene glycol (DEG) dialkyl ether, the diglycol monotertiary alkyl ether, the dipropylene glycol dialkyl ether, the dipropylene glycol monoalky lether, ester (ethyl acetate for example, butyl acetate, butyl glycol acetate, dibutyl ethylene glycol ethyl ethers acid esters, diethylene glycol (DEG) alkyl ether acetic acid esters, dipropylene glycol alkyl ether acetic acid esters, propylene glycol alkyl ether acetic acid ester, DBE), ether (for example oxolane), polyalcohol (glycerine for example, ethylene glycol, propylene glycol, neopentyl glycol), ketone (acetone for example, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone), hydrocarbon (cyclohexane for example, ethylo benzene, toluene, dimethylbenzene), DMF, the N-N-methyl-2-2-pyrrolidone N-, water, and their mixture.

Under the situation of liquid matrix material (for example liquid epoxies, acrylate), corresponding viscosity can be in addition by the adjustment during using, or the combination measure adjusting by solvent and temperature.

Dispersion can further contain the dispersant component.This comprises one or more dispersants.

In principle, as well known to those skilled in the artly be used for dosed dispersion and disclosed in the prior art all dispersants are suitable.Preferred dispersing agent is surfactant or surfactant mixture, for example anion, cation, both sexes or non-ionic tenside.

Cation and anion surfactant are for example referring to " Encyclopedia of PolymerScience and Technology (polymer science technology encyclopedia) ", J.Wiley﹠amp; Sons (1966), the 5th volume, 816-818 page or leaf and " Emulsion Polymerization and EmulsionPolymers (emulsion polymerisation and emulsion polymer) ", P.Lovell and M.EI-Asser edit, Wiley﹠amp; Sons (1997), the 224-226 page or leaf.

Also can use and well known to a person skilled in the art that the polymer with pigment affinity anchor group is as dispersant.

The consumption of dispersant can be 0.01-50 weight %, based on the total weight meter of dispersion.This ratio is 0.1-25 weight % preferably, preferred especially 0.2-10 weight %.

Dispersion of the present invention can contain filler component in addition.This can comprise one or more fillers.For example, but the filler component of the material of plating can contain the filler of fiber, layer or particulate forms, or their mixture.These preferably can be from the commodity of commerce acquisition, for example inorganic filler.

Can use filler or reinforcing agent in addition, for example glass powder, inorfil, whisker, aluminium hydroxide, metal oxide (for example aluminium oxide or iron oxide), mica, quartz powder, calcium carbonate, magnesium silicate (talcum), barium sulfate, titanium dioxide or wollastonite.

Can use other additive in addition, for example thixotropic agent, for example silicon dioxide, silicate, for example silica gel or bentonite; Or organic thixotropic agent and thickener, for example polyacrylic acid, polyurethane, hydration castor oil, dyestuff, aliphatic acid, fatty acid amide; Plasticizer, lattice reagent, defoamer, lubricant, drier, crosslinking agent, light trigger, chelating agent, wax, pigment, conducting polymer particle.

The ratio of filler component is 0.01-50 weight % preferably, based on the total weight meter of dry coating.This ratio is more preferably 0.1-30 weight %, preferred especially 0.3-20 weight %.

In addition, dispersion of the present invention can also contain processing aid and stabilizer, for example UV stabilizer, lubricant, anticorrisive agent and fire retardant.Their ratio is 0.01-5 weight % normally, based on the total weight meter of dispersion.This ratio is 0.05-3 weight % preferably.

Contain by use in basis material can not have that electropaining is covered and/or after dispersion of nano-particles body that electrolysis applies was administered to basic unit on the base material, basis material was solidified at least in part and/or is dry.Dry and/or curing is carried out according to conventional method.For example, basis material can solidify according to chemical mode, for example, for example undertaken by UV radiation, electron radiation, wave radiation, IR radiation or temperature by polymerization, addition polymerization or the polycondensation of basis material, or by evaporating solvent and purely according to the chemical mode drying.By the combination of physics and chemical mode carry out drying also be also can.

By using the particle of mean particle diameter, preferably after using, carry out extra Temperature Treatment so that particles sintering is in the same place with dry described layer less than 100nm.This Temperature Treatment be generally 80-300 ℃, preferred 100-250 ℃, particularly carried out 1-60 minute, preferred 2-30 minute and especially 4-15 minute under the temperature in 180-200 ℃ of scope.

In one embodiment, at least in part dry or solidify after, contained the not having particle that electropaining is covered and/or electrolysis applies comes out at least in part in dispersion, make it possible to obtain not have the nucleation site that electropaining is covered and/or electrolysis applies, can the plated metal ion on this position, thus cover and/or electrolysis forms metal level during applying in no electropaining subsequently.If described particle is formed by the material of oxidation, then also must remove oxide skin(coating) in advance at least in part sometimes.According to the mode of implementing the method, when for example using acidic electrolyte solution to implement, the removal of oxide skin(coating) can be carried out simultaneously with washing technology, does not need extra procedure of processing.

In the advantage that no electropaining is covered and/or electrolysis exposes described particle before applying be: in order to obtain continuous conductive surface, by exposing described particle, coating only needs to contain a certain proportion ofly can not have the particle that electropaining is covered and/or electrolysis applies, and the situation of this ratio when not exposing particle hanged down about 5-15 weight %.Other advantage is that the coating of being produced has uniformity and continuity and high reliability of technology.

Can not have that electropaining is covered and/or particle that electrolysis applies can mechanically expose, for example spray by pulverizing, grinding, milling, sand milling or with supercritical carbon dioxide; Expose with physics mode, for example by heating, laser, ultraviolet light, corona or plasma discharge; Or expose with chemical mode.Under the situation of Chemical exposure, chemicals or chemical mixture that preferred use can be compatible with basis material.Under the situation of Chemical exposure, basis material can dissolve from the teeth outwards and be washed off at least in part, for example carries out with solvent; Or the chemical constitution of basis material can make that not having the particle that electropaining is covered and/or electrolysis applies comes out at least in part with suitable reagent destruction.Can make the reagent of basis material swelling be applicable to that also exposure can not have the particle that electropaining is covered and/or electrolysis applies.This swelling has formed the space, deposited metal ions to enter this space from electrolyte solution, and what make more number more can not have electropaining is covered and/or electrolysis applies particle by washing.The method that significantly is better than prior art subsequently by adhesiveness, uniformity and the continuity of metal level of not having electricity and/or electrolysis mode deposition.The processing speed of metallizing is also higher, and this is because more the particle that electropaining is covered and/or electrolysis applies that can not have of more number comes out, and makes it possible to achieve extra cost advantage.

If basis material is for example epoxy resin, modified epoxy, epoxy-novolac resin, polyacrylate, ABS, Styrene-Butadiene or polyethers, then can there be electropaining is covered and/or electrolysis applies particle preferably by using oxidant to expose.Oxidant has destroyed the bonding of basis material, makes adhesive dissolve, thereby exposes described particle.Suitable oxidant is for example manganate, for example potassium permanganate, potassium manganate, sodium permanganate, sodium manganate, hydrogen peroxide, oxygen; Oxygen in the presence of catalyst, catalyst are for example manganese salt, molybdenum salt, bismuth salt, tungsten salt and cobalt salt; Ozone, vanadium pentoxide, selenium dioxide, ammonium polysulfide solution, the sulphur in the presence of ammonia or amine, manganese dioxide, potassium ferrate, bichromate/sulfuric acid, the chromic acid in sulfuric acid or acetate or acetic anhydride, nitric acid, hydroiodic acid, hydrobromic acid, dichromic acid pyridine, chromic acid-pyridine complex, chromic anhybride, chromium oxide (VI), periodic acid, lead tetraacetate, quinone, the methyl quinone, anthraquinone, bromine, chlorine, fluorine, iodine (III) salting liquid, dithionate solution, SODIUM PERCARBONATE; The salt of oxygen hydracid, for example chlorate or bromate or iodate; The salt of high hydracid, for example sodium metaperiodate or sodium perchlorate; Sodium perborate; Bichromate, for example sodium dichromate; The salt of persulfuric acid, for example potassium peroxydisulfate, permonosulphuric acid potassium; Chloro chromic acid pyridine; The salt of hypohalogenous acids, for example clorox; Dimethyl sulfoxide (DMSO) in the presence of electrophilic reagent, t-butyl hydroperoxide, 3-chlorine benzylhydroperoxide salt, 2,2-dimethyl propionic aldehyde, the high iodine alkane of Des-Martin, oxalyl chloride, perhydrit adduct, perhydrit, 2-iodoso benzoic acid, permonosulphuric acid potassium, metachloroperbenzoic acid, N-methylmorpholine-N-oxide, 2-methyl-third-2-base hydroperoxides, peracetic acid, neovaleraldehyde, osmium tetroxide, oxone, ruthenium (III) and (IV) salt are 2,2,6, oxygen under 6-tetramethyl-piperidyl-N-oxide exists, the high iodine alkane of triacetyl oxygen base, trifluoroperacetic acid, trimethyl-acetaldehyde, ammonium nitrate.Temperature during this process can randomly improve, thereby improves process-exposed.

Preferred oxidant is a manganate, for example potassium permanganate, potassium manganate, sodium permanganate, sodium manganate, hydrogen peroxide, N-methylmorpholine-N-oxide; Percarbonate, for example SODIUM PERCARBONATE or potassium percarbonate; Perborate, for example sodium perborate or potassium perborate; Persulfate, for example sodium peroxydisulfate or potassium peroxydisulfate; Peroxide two-and sodium salt, sylvite and the ammonium salt of sulfate mono; Clorox; The perhydrit adduct; The salt that contains the oxygen hydracid, for example chlorate or bromate or iodate; The salt of high hydracid, for example sodium metaperiodate or sodium perchlorate; Peroxo disulfate acid TBuA, quinone, iron (III) salting liquid, vanadium pentoxide, dichromic acid pyridine, hydrochloric acid, bromine, chlorine, bichromate.

Particularly preferred oxidant is a potassium permanganate, potassium manganate, sodium permanganate, sodium manganate, hydrogen peroxide and its adduct, perborate, percarbonate, persulfate, peracetic dithionite, clorox and perchlorate.

To contain ester structure for example and for example can not have the particle that electropaining is covered and/or electrolysis applies in the basis material of mylar, polyester acrylate, polyether acrylate, polyester-polyurethane in order to be exposed to, preference is as using the chemicals and/or the chemical mixture of acidity or alkalescence.Preferred acidic chemical and/or chemical mixture are the acid that for example concentrates or dilute, for example hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid.According to basis material, organic acid also is suitable, for example formic acid or acetate.Suitable alkaline chemical and/or chemical mixture are alkali for example, for example NaOH, potassium hydroxide, ammonium hydroxide, or carbonate, for example sodium carbonate, calcium carbonate.

Temperature in this process can randomly raise to improve process-exposed.

What solvent also can be used for being exposed to basis material can not have the particle that electropaining is covered and/or electrolysis applies.Solvent must be complementary with basis material, and this is because basis material must be dissolved in the solvent or by solvent swell.When using when can dissolve the solvent of basis material, basic unit only contact the short time with solvent so that the upper strata of basis material by solvation, thereby dissolve.Preferred solvent is dimethylbenzene, toluene, halogenated hydrocarbons, acetone, methyl ethyl ketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK), diethylene glycol monobutyl ether.Temperature between breaking-in period can randomly raise to improve solubility behavior.

In addition, also can use mechanical means to expose and not have the particle that electropaining is covered and/or electrolysis applies.Suitable mechanical means is for example to pulverize, grind, spray the sprinkling of pressurizeing, sandblast or spray with supercritical carbon dioxide with abrasive polishing or water.The top layer of the structuring basic unit that has cured and print is removed by this mechanical means respectively.Thereby expose contained the not having particle that electropaining is covered and/or electrolysis applies in basis material.

Well known to a person skilled in the art that all abrasive materials can be as the abrasive material of polishing usefulness.Suitable abrasive material is a ground pumice for example.For the top layer by the dispersion after solidifying with removal with the pressurization sandblast, water spray preferably contains a spot of solids, for example ground pumice (Al ₂O ₃), its average particle size distribution is the 40-120 micron, preferred 60-80 micron; And silica flour (SiO ₂), its particle diameter is greater than 3 microns.

Do not contain already oxidised material if can there be the particle that electropaining is covered and/or electrolysis applies, then in preferred embodiments, before forming metal level in the basic unit of structurized or face width, remove oxide skin(coating) at least in part.In this case, oxide skin(coating) can for example be removed by chemical mode and/or mechanical system.Handling basic unit not remove the operation of oxide skin(coating) from there being the particle that electropaining is covered and/or electrolysis applies by chemical mode, the material that is applicable to described processing is for example acid, for example concentrated or dilute sulfuric acid, perhaps concentrated or dilute hydrochloric acid, citric acid, phosphoric acid, acylamino-sulfonic acid, formic acid, acetate.

The suitable mechanical method that is used for removing oxide skin(coating) from the particle that can not have that electropaining is covered and/or electrolysis applies is generally identical with the mechanical means that is used to expose described particle.

The basic unit preferably painting method of the well-known by routine uses with dispersion.These painting methods for example are that curtain coating, lacquer are coated with, scraper coating, spraying, dip-coating, roller coat etc.As another selection, also can adopt any printing process that basic unit is printed onto on the carrier.The printing process of printed substrate is for example roll marks or sheet printing process, and for example silk screen printing, intaglio, aniline printing, type printing, backing plate printing, ink jet printing, DE10051850 are described

Method, hectographic printing or magnetic variation printing.But, also can use any other printing process that well known to a person skilled in the art.The layer thickness of the basic unit that produces by described painting method or printing is the 0.01-50 micron preferably, more preferably 0.05-25 micron, preferred especially 0.1-15 micron.These layers can be coated on the whole surface or with structured way and apply.Also can use a plurality of layers by adjoining land.

According to printing process, can directly print different fine structures.

Dispersion preferably stirred or pumping in reservoir vessel before using.Stirring and/or pumping prevent may precipitating of described particle contained in dispersion.In addition, also advantageously dispersion is carried out thermal conditioning in reservoir vessel.This makes and can basic unit be impressed on the carrier in improved mode that this is owing to can regulate constant viscosity by thermal conditioning.Thermal conditioning especially for example stir and/or during pumping the energy input heating dispersion by blender or pump be necessary, so its viscosity changes.In order to improve flexibility and for the cost reason, digital print methods shown for example

Method is suitable under the situation that printing applies especially.These methods have avoided producing the cost of printing stencil usually, for example print roller or silk screen, and in the time need printing multiple different structure in succession, avoided frequent variation.In digital print methods shown, can change along with new design immediately, do not need re-assemble time and shut-down.In the time will carrying out the structuring printing consistently with identical setting, conventional printing process is preferred, for example intaglio, hectographic printing, silk screen printing or magnetic variation printing process.

In this case, no electropaining is covered and/or electrolysis applies to use and well known to a person skilled in the art that any method carries out.Can use the metal coating of any routine in addition.In this case, the composition that is used to the electrolyte solution that applies depends on the metal that will be used for coated with conductive structure on base material.In principle, all metals can be used to not have that electropaining is covered and/or electrolysis applies.Cover and/or the common metal of electrolysis coating deposition on conductive surface is for example gold, nickel, palladium, platinum, silver, tin, copper or chromium by no electropaining.The thickness of one or more layers sedimentary deposit is in and well known to a person skilled in the art in the normal ranges.Under the situation that no electropaining is covered, can use all metals more senior than the lowermost level noble metal of dispersion.

The electrolyte solution that is applicable to the coated with conductive structure is well known to a person skilled in the art, for example referring to Werner Jilek, Gustl Keller, Handbuch der Leiterplattentechnik[printed circuit technique handbook], Eugen G.Leuze Verlage, 2003, the 4 editions, the 332-352 page or leaf.

Under the situation that electrolysis applies, for example in order to produce metal level, general, the base material that is applied by dispersion at first is sent in the bath that contains electrolyte solution.Base material is carried through bathing then, wherein contacts contained the not having particle that electropaining is covered and/or electrolysis applies in the basic unit that formerly uses by at least one negative electrode.Here, can use and well known to a person skilled in the art any suitable conventional negative electrode.As long as negative electrode contacts with basic unit, metal ion just deposits to form metal level in described basic unit from electrolyte solution.

In basic unit, formed after the metal level carrier of making by non-conductive material on the lamination.In a preferred embodiment, the plastic non-conductive material that for this reason will be used for producing carrier is administered to the metal level that makes in step (c).Plastic non-conductive material preferably provides with the form of the plasticity sheet of semi-solid preparation.The plasticity sheet of semi-solid preparation preferably is enhanced.The plasticity sheet in addition preferably solid and touch dried, so can handle routinely.The operation that the material that will be used for carrier is administered on the metal level is manual carrying out, or by well known to a person skilled in the art that automatic mode carries out.

Select as another, also the plastic non-conductive material that is used to produce carrier can be provided being administered to metal level as viscous liquid or as thickener, or to be provided by the form of the fiber of resin impregnation or pad.The material that is used for carrier is used by well known to a person skilled in the art any application process.Suitable application process be for example coat with lacquer be coated with, curtain coating, scraper coating, spraying, roller coat or printing.Under the situation of fiber or pad, use preferably and undertaken by placement.

Provide with the thickener form if be used for the material of carrier, then preference as by printing, curtain coating, roller coat, extrude or scraper apply with as described in material be administered on the metal level.

In order to improve the bonding of the metal level that on carrier, applies, if necessary, carrier and/or metal level can be before the lamination metal level by well known to a person skilled in the art that method carries out preliminary treatment, for example by using extra bonding or adhesive phase.As adhesion promotor, for example can use so-called based on NaClO ₂The black of/NaOH or brown oxide, silane or polyethyleneimine: amine aqueous solution, for example from the Lupasol brand product of BASF AG, or commercially available adhesion promotor.

If be provided at upside and downside all have metal level by the substrate laminated material of washing, then after using plastic non-conductive material, another base material with metal level is placed on the plastic non-conductive material, makes metal level contact with the material that is used for carrier.If only provide a side have metal level by the substrate laminated material of washing, base material that then will not use metal level is placed into the material that is used for carrier.As mentioned above, in this case, base material is preferably applied by release agent so that release agent between base material and metal level, or is made by release agent.The lamination of carrier on metal level generally undertaken by compacting at high temperature.Temperature is preferably in 120-250 ℃ of scope.

Be used to suppress be in the material between the base material pressure preferably in 0.1-100 crust scope, 5-40 crust particularly.

Being cured to form by the time of the substrate laminated material of washing generally is 1-360 minute, preferred 15-220 minute, and preferred 30-90 minute especially.

The suitable material that is used for carrier is for example any enhancing or the polymer that do not strengthen, for example conventional those of printed circuit board (PCB) of being used for.Suitable polymers is for example difunctionality or polyfunctional bisphenol-A or Bisphenol F resin, epoxy-novolac resin, brominated epoxy resin, cycloaliphatic epoxy resin, bismaleimides-cyanate resin, polyimides, phenol resin, cyanate, melamine resin or amino resins, phenoxy resin, allylation polyphenylene oxide (APPE), polysulfones, polyamide, organosilicon and fluororesin, and their composition.The material that is used for carrier can for example contain in addition and well known to a person skilled in the art additive, for example crosslinking agent and catalyst, for example polyamines of tertiary amine, imidazoles, aliphatic series and aromatics, polyamino amine, acid anhydrides, BF ₃-MEA, phenol resin, phenylethylene-maleic anhydride polymer, hydroxy acrylate, dicyandiamide or polyisocyanates; And fire retardant and filler, for example inorganic filler, for example talcum, phyllosilicate, aluminium oxide, aluminium hydroxide or glass.

In addition, conventional other polymer and additive also is suitable in printed circuit board industry.

In order to produce electronic printing circuit board, the preferred carrier that strengthens that uses.The suitable filler that is used to strengthen is for example paper, glass fibre, glass nonwoven fabrics, glass fabric, aramid fibre, aramid nonwoven fabric, aromatic poly-amide fabric, PTFE fabric, PTFE paillon foil.

According to produce by the thickness of the substrate laminated material of washing, it can be hard or soft after compacting.

A plurality of by the substrate laminated material of washing in order to produce simultaneously, in preferred embodiments, multi-layer substrate that will be applied by metal level and plastic non-conductive material alternately piled up before lamination each other.In this case, must guarantee in the time will producing the substrate laminated material that on both sides, all has metal level that these sides that scribbled the base material of metal level contact with plastic non-conductive material respectively.As mentioned above, base material preferably has release agent so that release agent is between base material and the metal level, is perhaps made by release agent.By using the release agent coated substrate, then after carrier had been laminated on the metal level, carrier can be removed from base material with metal level.

In order to produce by the substrate laminated material of washing, the base material stacked body with metal level and plastic non-conductive material is suppressed.For this reason, for example, stacked body is introduced the opening of hydraulic press between the heating and pressurizing plate, and according to well known to a person skilled in the art that being used for the conventional process sequence of making base material further processes.

Metal level on base material can have adhesion promotor, thus provide and carrier between bonding.Adhesion promotor can be black or the brown oxide that is purchased, or uses silane lacquer, and the polyethyleneimine: amine aqueous solution, for example from the Lupasol brand product of BASF AG.

Compacting is generally carried out under the pressure of 0.1-100 crust, preferred 5-40 crust.When using can be with the plastic non-conductive material of hot setting the time, suppress and preferably at high temperature carry out.Selected temperature depends on employed material.Preferably 100-300 ℃ of temperature, preferred 120-230 ℃ especially.For example, standard FR4 epoxy-resin systems contracts 175-180 ℃ temperatures.More highly cross-linked system need be up to 225 ℃ temperature.For these resins, pressing pressure is preferably selected between 15 crust and 30 crust.

During pressing, plastic non-conductive material preferably solidifies at least in part.In this way, will after compacting, be formed by the substrate laminated material of washing, and can further process.

The thickness of carrier will be set by amount, its resin content and the pressing pressure of plastic non-conductive material.Produce in this way by the surface quality of the substrate laminated material of washing generally corresponding to the surface appearance of base material.

By with base material structuring suitably, basic unit can be in turn laminated on the carrier in structurized mode.This will simplify processing subsequently, for example produce printed circuit board (PCB).

After non-conductive material has been in turn laminated on the metal level, remove the carrier of metal level with lamination and optional at least a portion basic unit from base material.Because, be applied to contain can not have that electropaining is covered and/or dispersion of nano-particles body that electrolysis applies on metal level will can not replace this dispersion fully sometimes, so after carrier had been laminated on the metal level, the upside of carrier had the layer that can not have the particle that electropaining is covered and/or electrolysis applies that randomly also contains in basis material.Continuous metal level is to carrier.In order to be implemented in the continuous conductive layer on the carrier in one embodiment, after removing carrier with lamination metal level, in another step, preferably can not have electropaining is covered and/or electrolysis applies particle deposit to the bonding basic unit of carrier on.This is undertaken by well known to a person skilled in the art conventional method.Before the no electricity and/or electrolytic deposition of metal, contained the not having particle that electropaining is covered and/or electrolysis applies (it is bonding with the metal level that is laminated on the carrier) preferably comes out after removing the sheet that scribbles release agent at least in part in basic unit.Can not have that electropaining is covered and/or particle that electrolysis applies comes out in this case, this with the dispersion that is administered to as mentioned above on the base material in can not have that electropaining is covered and/or the exposure of the particle of electrolysis coating is similar.

Because no electricity and/or the electrolytic deposition of metal in the basic unit that is in turn laminated on the carrier obtained continuous conductive metal layer.

In another embodiment, remove basic unit's remainder that may exist.For this reason, make basic unit carry out not have the described corresponding processing of particle that electropaining is covered and/or electrolysis applies about exposing with top.With can not have that electropaining is covered and/or the exposure of the particle that electrolysis applies identical, removing also of basic unit can be carried out according to chemical mode or mechanical system.Processing will be carried out being dissolved fully or removing up to basis material.In this way, contained not the having in this layer that still the keeps particle that electropaining is covered and/or electrolysis applies also is removed.It is remaining that what get off is by the metal simple metal layer that has that electropaining is not covered and/or electrolysis applies.

In compacting with solidify on plastic non-conductive material and the lamination after the metal level the preferred further processing of the substrate laminated material of metallizing in this way.For example, can will be carried out classification by the substrate laminated material of washing.For this reason, each layer can be cut into sheet with preliminary dimension.

Conductive structure is the metal level production from using preferably.Conductive structure is generally by well known to a person skilled in the art method production.Suitable method is for example plasma etching, photoresist method or laser ablation methods.

By accompanying drawing the present invention is described in more detail below, wherein:

Fig. 1 has shown a kind of technological process that metal level is administered on the base material that is applied by release agent,

Fig. 2 shown metal level has been laminated on the carrier,

Fig. 3 has shown that the basic unit with lamination is coated on the carrier.

Fig. 1 has shown metal level has been administered on the base material that is applied by release agent.

To contain can not have that electropaining is covered and/or dispersion of nano-particles body 5 that electrolysis applies is administered on the flat substrates 3 that is applied by release agent 1.Containing can not have that electropaining is covered and/or dispersion of nano-particles body that electrolysis applies can be administered on the base material 3 that is applied by release agent 1 by any method that well known to a person skilled in the art.Here in the embodiment of Miao Shuing, under the help of roller 7 dispersion 5 is being administered on the base material 3 that has been applied by release agent 1, its central roll 7 loads dispersion 5.For downside, preferably roller 7 is immersed in the containers 9 so that roller 7 is applied by this dispersion with dispersion 5 coated substrates 3.By contacting with the base material 3 that is applied by release agent 1, a part of dispersion 5 is transferred on the base material 3 from roller 7.On the base material 3 that is applied by release agent 1, formed basic unit 11.

In order to apply the upside of the base material 3 that is applied by release agent 1, for example dispersion 5 can be administered on the roller 7 from container 13, be administered on the base material 3 that is applied by release agent 1 from roller 7 then.Wherein in the method that under the help of roller 7 dispersion 5 is administered on the base material 3 that has been applied by release agent 1, any can realization with the whole surface of release agent 1 coated substrate 3 or other method of structuring coating also be suitable except described herein.If wish to obtain the structuring coating, then preferably use printing process.

The upside of the base material 3 that is applied by release agent and downside can be simultaneously or adjoining land coated.

Base material 3 can be a hard or soft.Select as another, replacement also can be used paper tinsel as the base material 3 that sheet provides.Under the situation of continuous processing control, paper tinsel preferably provides as the paper tinsel for no reason that is used for volume to volume technology.

After using basic unit 11, dry at least in part and/or curing at least in part with it.This for example realizes by being exposed to IR radiator 15.According to the basis material of dispersion 5, well known to a person skilled in the art and to solidify at least in part and/or any other method of dry basic unit 11 also is suitable.These methods are described hereinbefore.

Solidify at least in part and/or dry at least in part basic unit 11 after, make preferably that contained the not having particle that electropaining is covered and/or electrolysis applies exposes at least in part in basic unit 11.This for example is by carrying out with the solution washing that contains potassium permanganate.Select as another, above-mentioned any other oxidant or solvent also can be used to expose can not have the particle that electropaining is covered and/or electrolysis applies.Exposure is for example undertaken by spraying basic unit 11 with oxidant, and oxidant for example is a potassium permanganate.Can not have that electropaining is covered and/or the exposure of the particle that electrolysis applies is carried out in region of activation 17, here only schematically show.After exposing is washing process, thereby from being removed residual oxidizer or solvent by the base material 3 of basic unit 11 and release agent 1 coating.This carries out in scrubbing section 19, equally here schematically shows.

After the washing, electropaining is covered and/or the basic unit 11 of the particle that electrolysis applies is applied by metal level by no electricity and/or electrolysis mode to have not having of now having exposed in scrubbing section 19.This carries out in coating area 21.In this case, no electropaining cover and/or electrolysis apply can be according to well known to a person skilled in the art that any method carries out.After the coating area 21 generally is second scrubbing section 23.In second scrubbing section 23, washed out from the electrolyte residue that no electropaining is covered and/or electrolysis applies.

Be used to not have the electrolyte solution that electropaining is covered and/or electrolysis applies and generally do not sprayed, as shown in Figure 1, but will be immersed in the electrolyte solutions by the base material 3 of release agent 1 and basic unit's 11 coatings.But, well known to a person skilled in the art also to be suitable by any other method of no electricity and/or electrolysis mode coating basic unit 11.In basic unit 11 can not have that electropaining is covered and/or particle that electrolysis applies also can expose by immersing in oxidant or the solution.Also can be not by spraying base material 3 but by washing in the immersion wash solution.Any other appropriate method that well known to a person skilled in the art also can be used for exposing from basic unit 11 and can not have the particle that electropaining is covered and/or electrolysis applies and be used to wash the base material 3 that is applied by release agent 1 and basic unit 11.

Cover and/or after electrolysis applies in no electropaining, base material 3 by release agent 1, contain and can not have that electropaining is covered and/or the basic unit 11 of the particle that electrolysis applies and metal level 25 apply.

In order to produce, the non-conductive material that is used to form carrier is put on the base material 3 that applies in this way by the substrate laminated material of washing.

For production substrate laminated material, carrier is in turn laminated on the metal level 25.This is preferably undertaken by compression, as shown in Figure 2.

In order to produce by the substrate laminated material of washing, stacked body 35 is remained between first template 31 and second template 33 of press (for example hydraulic press), wherein in stacked body 35, by release agent 1, contain and can not have that electropaining is covered and/or base material 3 that the basic unit 11 of the particle that electrolysis applies and metal level 25 apply and plastic non-conductive material 37 alternately separate each other.Certainly, this stacked body also can contain the only coated base material 3 of one deck.If the method is carried out continuously and is used paper tinsel replacement base material 3 for no reason, then preferably stacked body is added between two rollers, thus compression.

As mentioned above, plastic non-conductive material 37 is the plastic materials that for example strengthen or do not strengthen, for example the epoxy resin of glass fibre enhancing.The terminal point of stacked body 35 is by only not had by being contained that electropaining is covered and/or the basic unit 11 of the particle that electrolysis applies and formed by the upper substrate 39 that metal level 25 applies in a side.In this case, basic unit 11 and metal level 25 are directly towards plastic non-conductive material 37.The bottom terminal point of stacked body 35 forms by lower substrate 41, and lower substrate 41 is applied by basic unit 11 and metal level 25 in a side only too, and wherein basic unit 11 and metal level 25 are towards the direction of plastic non-conductive material 37.But for the reason of production technology, upper substrate 39 and lower substrate 41 also can have basic unit 11 and metal level 25 at their upside and downside.Upper substrate 39 and lower substrate 41 be sheet material preferably.

Top suppresses plate 43 between the upper substrate 39 and second template 33, and the bottom suppresses plate 45 between the lower substrate 41 and first template 31.

For from plastic non-conductive material 37, metal level 25 with contain and not have that electropaining is covered and/or the basic unit of the particle that electrolysis applies 11 produces by the substrate laminated material of washing, first template 31 and second template 33 are applied press power.Thereby compacting stacked body 35.Applying by

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47 and 49 of press power schematically shows.By applying

press power

47,49, be included in by release agent 1, contain can not have that electropaining is covered and/or base material 3 that the basic unit 11 of the particle that electrolysis applies and metal level 25 apply between plastic non-conductive material 37 be compressed.Simultaneously, plastic non-conductive material 37 is solidified at least in part, forms the substrate laminated material.Because release agent 1, base material 3 can easily be removed after curing once more.This has stayed layer of metal layer 25 and some basic unit 11 of possibility on the non-conducting material that has solidified that forms carrier, basic unit 11 is contained can not have the particle that electropaining is covered and/or electrolysis applies.

Base material 3 preferably is made of metal.So base material 3 is good heat conductors, thereby heat also can be supplied to plastic non-conductive material 37, thereby realizes evenly solidifying at least in part.The compression of plastic non-conductive material 37 is preferably carried out under the temperature higher than ambient temperature.

Remove upper substrate 39 and more easily remove lower substrate 41 from bottom inhibition plate 47 in order more easily to suppress plate 43 from top, those of upper substrate 39 and lower substrate 41 are preferably also applied by release agent 1 in the face of the surface of top inhibition plate 43 and bottom inhibition plate 45 respectively.

After solidifying plastic non-conductive material 37 at least in part, discharge the press power 47,49 that has been applied on first template 31 and second template 33.Taking-up by the stacked body 35 of the base material 3 that is applied by release agent 1 and produced by the substrate laminated material of washing.The substrate laminated material by washing between the base material 3 that is applied by release agent 1 is removed subsequently.Because release agent 1, basic unit 11 can not adhere on the base material 3.So, remove base material 3 under the situation that can not sustain damage at the metal coating that comprises metal level 25 and basic unit 11 on the carrier.After removing by the substrate laminated material of washing, the base material 3 that is applied by release agent 1 is used to produce other once more by the substrate laminated material of washing.If release agent 1 is connected with base material 3 securely, for example by release agent 1 is adhered on the base material 3 with chemical mode, then base material 3 can be following directly utilizes again: using to contain not to have that electropaining is covered and/or the new basic unit 11 of the particle that electrolysis applies, cover by no electropaining subsequently and/or electrolysis applies metal level 25 is provided, and use other plastic non-conductive material 37 in the above.

If release agent 1 is not connected with base material 3 securely, then initial necessity is to use the layer of new release agent 1 before forming film in dosed dispersion 5.

Release agent 1 can be used by well known to a person skilled in the art any application process.For example, can be by plasma method, scrape the skill in using a kitchen knife in cookery, curtain coating, spraying, roller coat, printing, lacquer and method such as be coated with and use release agent 1.

Plastic non-conductive material 37 is preferably used with the form of the plasticity sheet of semi-solid preparation.Select as another, also can plastic non-conductive material 37 be positioned over by release agent 1 by the form of the fiber of resin impregnation or pad, contain can not have that electropaining is covered and/or the base material 3 of the basic unit 11 of the particle that electrolysis applies and metal level 25 coatings on.Placement is in this case carried out according to the mode of well known to a person skilled in the art.

In continuation method, not only preferably use paper tinsel for no reason to replace design base material 3 in blocks, and plastic non-conductive material preferably provide with the form of paper tinsel for no reason, it can be processed in the volume to volume method.

Behind pressing operation shown in Figure 2, sometimes may be necessary be have metal level 25 and optional have contain can not have that electropaining is covered and/or the carrier of the basic unit 11 of the particle that electrolysis applies on use other metal level.This is shown schematically among Fig. 3.

By lamination, metal level 25 is adhered on the non-conductive material that forms carrier 51.Carrier 51 forms by compressing and solidifying plastic non-conductive material 37.On the outside of carrier 51, containing can not have that electropaining is covered and/or the residue of the basic unit 11 of the particle that electrolysis applies or basic unit 11 may keep and is applied on the metal level 25.Because the particle 11 that electropaining is covered and/or electrolysis applies that can not have that is included in the basic unit 11 generally is not connected to each other, so may do not conducted electricity by the upside of the carrier 51 of washing.Therefore, what possibility was necessary is to use other metal level 53 in basic unit 11, or removes basic unit 11.Basic unit 11 can for example remove by chemical mode, for example in activating bath; Or remove mechanically, for example by scrubbing or sandblast.Other metal level 53 will be used by well known to a person skilled in the art method.Other metal level can comprise identical metal or different metals.In order to make the metal adhesion be used for other metal level 53 can not have to containing that electropaining is covered and/or the basic unit 11 of the particle that electrolysis applies, preferred at first the exposure can not have the particle that electropaining is covered and/or electrolysis applies.This generally carries out in region of activation 55.As mentioned above, exposure is for example undertaken by handling with oxidant or solvent in this case.Suitable solvent and oxidant are also as mentioned above.Select as another, can expose according to physics mode or chemical mode not to have the particle that electropaining is covered and/or electrolysis applies.If expose according to chemical mode, then can make activator for example oxidant or solvent can not have that electropaining is covered and/or the basic unit 11 of the particle that electrolysis applies contacts with containing, this is undertaken by sprinkling.Select as another, also the carrier 51 that has metal level 25 and basic unit 11 can be immersed in the activator.

After the particle that can not have that electropaining is covered and/or electrolysis applies has exposed, preferably wash out the residue of solvent or oxidant from the carrier 51 that is applied by basic unit 11 and metal level 25.This for example carries out in scrubbing section 57.In order to wash, carrier 51 can for example spray with washing agent, for example contains the acidic aqueous solution of hydrogen peroxide or contains the acid solution of hydroxyl ammonium nitrate.As another selection, for example, also can submergence carrier 51.After the scrubbing section 57 is coating area 59, and here, containing not to have that electropaining is covered and/or the basic unit 11 of the particle that electrolysis applies is covered according to no electropaining by other metal level 53 and/or the coating of electrolysis coating method.In this case, no electropaining is covered and/or the electrolysis coating can be according to well known to a person skilled in the art that any way carries out, and no electropaining is covered and/or the electrolysis coating generally will be carried out according to mentioned above.

In order to have removed the residue of electrolyte solution from the carrier 51 that covers in no electropaining and/or electrolysis has been applied by other metal level 53, the basic unit 11 that may still exist and metal level 25 after applying, the carrier 51 that has layer 25, a

possible layer

11,53 preferably in second scrubbing section 61 no electropaining cover and/or the electrolysis coating after wash.Washing general water carries out.

Enough thin contain can not have that electropaining is covered and/or the situation of the basic unit 11 of the particle that electrolysis applies under, contained the not having particle that electropaining is covered and/or electrolysis applies can cover and/or electrolysis applies and by the metal ion replacement from electrolyte solution by no electropaining in basic unit 11.In this case, be applied on the carrier 51 to totally continuous metal level 53 continuously basically.When metal level 25 when 53 are connected, this obtains the even continuous metal level on carrier 51.

Other metal level 53 of producing by the inventive method or evenly continuous metal level can have the thickness of any hope, this depends on does not have the mode that electropaining is covered and/or electrolysis applies.The inventive method is for producing at 0.1-25 micron, preferred 1-10 micron, especially being favourable for the layer thickness in the 2-6 micrometer range.

After using metal level 53, produce in this way by the substrate laminated material of washing (contain have

metal level

25 and 53 and the carrier 51 of optional basic unit 11) can further process.This is for example by well known to a person skilled in the art that the conventional method that is used for printed circuit board (PCB) carries out.

Substrate laminated material by washing of the present invention can be used for for example producing printed circuit board (PCB).These printed circuit board (PCB)s for example are those of inside and outside horizontal structure with multilayer, the lightly conducting hole, chip directly placed, soft and hard printed circuit board, and for example be installed in product such as computer, phone, TV, electronic car element, keyboard, broadcast receiver, recorder, CD, CD-ROM and DVD player, game machine, detection and conditioning equipment, transducer, electronics cooking apparatus, electronic toy etc.

Substrate laminated material by washing of the present invention can be further used for producing the RFID antenna, transponder antenna or other antenna structure, the chip card module, flat cable, seat heater, foil conductor, conducting wire in solar cell or LCD/ plasma panel, capacitor, sheet capacitance, resistance, transducer, fuse, or be used to produce any type of electrolysis coated product, for example by the polymer support with definite layer thickness of metal at the one or both sides plating, the interconnect equipment of 3D molding, or be used to produce ornamental or functional surface on product, they are used for for example electromagnetic radiation shielding, be used for heat conduction or as packaging material.In addition, the metal forming that is aggregated the thing coating also can be used to produce the contact on whole electronic component or touch pad or interconnection line, and is used to produce the antenna with organic electronic element connection.In addition, also can be applied to the mobile field of the bipolar plate in the fuel cell.In addition, also can produce full surface or structurized conductive layer, its follow-up decorative metals that is used for carrier applies, and for example is used for the ornamental member in automobile, amenities, toy, family expenses and office field, and packaging material and paper tinsel.In addition, can also be used to produce thin metal foil, battery paper tinsel or the polymer support of plating on one or both sides.The metal forming that is aggregated the thing coating also needing can be used for the field of good heat-conductivity, for example at the paper tinsel that is used for seat heater, underfloor heater and insulating material.

Of the present inventionly be aggregated metal forming that thing applies and be preferred for producing printed circuit board (PCB), RFID antenna, transponder antenna, seat heater, flat cable, non-contact type chip, thin metal foil or the polymer support of plating on one or both sides, foil conductor, conducting wire in solar cell or LCD/ plasma panel, or be used to produce decorative product, for example be used for packaging material.，

Reference numerals list

1 releasing agent

3 base materials

5 dispersions

7 rollers

9 containers

11 basic units

13 containers

The 15IR source

17 region of activations

19 scrubbing sections

Before 21 coatings

23 second scrubbing sections

25 metal levels

31 first templates

33 second templates

35 stacked bodies

37 plastic non-conductive materials

39 upper substrate

41 lower substrate

43 tops suppress plate

45 bottoms suppress plate

47,49 press powers

51 carriers

53 metal levels

55 region of activations

57 scrubbing sections

59 coating areas

61 scrubbing sections

Claims

A production have the carrier (51) made by non-conductive material (37), by the method for the substrate laminated material of washing, applied by metal level (25,53) at least one side of described carrier, the method may further comprise the steps:

(a) with dispersion (5) basic unit (11) is administered on the base material (3), described dispersion (5) contains can not have that electropaining is covered and/or particle that electrolysis applies in basis material,

(b) solidify at least in part and/or dry described basis material,

(c) cover by no electropaining and/or electrolysis is coated in basic unit (11) and go up forms metal level (25),

(d) will be laminated to by the carrier (51) that make non-conductive material (37) on the metal level (25) that in step (c), makes,

(e) remove with the carrier (51) of metal level (25) lamination and at least a portion basic unit (11) randomly from base material (3).
2. the process of claim 1 wherein sheet (3) or the paper tinsel that base material is applied by release agent.
3. the process of claim 1 wherein that base material is sheet or the paper tinsel of being made by release agent.
4. each method among the claim 1-3 is wherein being removed base material (3) afterwards, according to chemical mode or mechanical system remove be in turn laminated to carrier (51) on the basic unit (11) that is connected of metal level (25).
5. each method among the claim 1-3, wherein in step (e), remove base material (3) afterwards, in another step with metal according to no electricity and/or electrolysis mode deposit to be in turn laminated to carrier (51) on the basic unit (11) that is connected of metal level (25) on.
6. each method among the claim 1-5, wherein the no electropaining in step (b) is covered and/or before electrolysis applies, can not had the particle that electropaining is covered and/or electrolysis applies and exposed at least in part.
7. claim 5 or 6 method, wherein be in turn laminated to carrier (51) on the basic unit (11) that is connected of metal level (25) in contained the not having particle that electropaining is covered and/or electrolysis applies in exposure at least in part from base material (3) is removed after.
8. claim 6 or 7 method can not have wherein that electropaining is covered and/or the exposure of the particle that electrolysis applies is undertaken by chemical mode, physics mode or mechanical system.
9. each method among the claim 6-9 can not have wherein that electropaining is covered and/or the exposure of the particle that electrolysis applies is carried out with oxidant.
10. the method for claim 9, wherein oxidant is potassium permanganate, potassium manganate, sodium permanganate, sodium manganate, hydrogen peroxide or its adduct, perborate, percarbonate, persulfate, peracetic dithionite, clorox or perchlorate.
11. the method for claim 6 or 7, can not have wherein that electropaining is covered and/or the exposure of the particle that electrolysis applies be by can dissolving, the effect of the material of etching and/or the described basis material of swelling carries out.
12. the method for claim 11 wherein can dissolving, the material of etching and/or the described basis material of swelling is acid or alkaline chemicals or chemical mixture, or solvent.
13. each method among the claim 1-12, wherein the no electropaining in step (c) cover and/or electrolysis apply before and/or removing base material (3) afterwards in another step no electropaining cover and/or the electrolysis metallizing before, electropaining is covered and/or the particle of electrolysis coating is not removed the oxide skin(coating) of any existence from having.
14. each method among the claim 1-13 wherein is administered to basic unit (11) on the base material (3) in the mode on structured way or whole surface by painting method.
15. the method for claim 14, wherein painting method is printing, curtain coating, roller coat or spraying method.
16. each method among the claim 1-15 wherein stirred dispersion or pumping in reservoir vessel before using.
17. each method among the claim 1-16 wherein is administered to metal level (25,53) upside and the downside of carrier (51).
18. each method among the claim 1-17, wherein in step (d), the lamination of the carrier of being made by non-conductive material (51) is undertaken by compacting.
19. the method for claim 18, wherein compacting is what to carry out under the temperature higher than ambient temperature.
20. the method for claim 18 or 19, wherein multilayer was alternately piled up before compacting each other by the sheet (3) of release agent (1) and basic unit (11) coating and the carrier of being made by non-conductive material (51).
21. each method among the claim 1-20, wherein carrier (51) is administered to the sheet (3) that is applied by release agent (1) and basic unit (11) that is used at step (d) lamination with the form of viscous liquid.
22. each method among the claim 1-20, wherein carrier (51) be administered to by the form of the fiber of resin impregnation or pad or the plasticity sheet that not exclusively solidifies be used for step (d) lamination by the sheet (3) of release agent (1) and basic unit (11) coating.
23. each method among the claim 1-22, wherein carrier (51) solidifies during lamination at least in part.
24. each method among the claim 1-23, wherein release agent (1) is by using releasing agent layer or being applied on the sheet (3) by applying with the dispersion that contains release agent.
25. each method among the claim 1-24, wherein release agent (1) is applied on the sheet (3) by plasma method.
26. each method among the claim 1-25, wherein release agent (1) has the surface tension with respect to air less than 25mN/m.
27. each method among the claim 1-26, wherein release agent (1) is to be selected from polyvinyl alcohol, organosilicon polymer, fluoropolymer, low-molecular-weight fat, wax or oil.